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37 results on '"Matthieu, Courty"'

1. Structural and Vibrational Investigations of Mixtures of Cocoa Butter (CB), Cocoa Butter Equivalent (CBE) and Anhydrous Milk Fat (AMF) to Understand Fat Bloom Process

Author

Mustapha El Hadri, Serge Bresson, Albane Lecuelle, Fatiha Bougrioua, Vincent Baeten, Van Hung Nguyen, Vincent Faivre, and Matthieu Courty

Subjects
cocoa butter (CB), cocoa butter equivalent (CBE), milk fatty acid (AMF), MIR and Raman spectroscopy, X-ray diffraction, Technology, Engineering (General). Civil engineering (General), TA1-2040, Biology (General), QH301-705.5, Physics, QC1-999, Chemistry, QD1-999
Abstract

Some studies found that the proportions of cocoa butter (CB), cocoa butter equivalent (CBE) and milk fatty acid (AMF) tend to influence the blooming delay when mixing them. The goal of our research is to determine the effects of the proportion of CB, CBE and AMF on the structural organization of the final mixtures. X-ray, DSC, MIR and Raman spectroscopy were used to analyze the structural features and the vibrational modes of four mixtures: CB + 0.5AMF, CB + AMF, CB + 0.5AMF + CBE and CB + AMF + CBE. At room temperature, the triglycerides are ingredients of CB, and CBE and AMF do not fully exhibit the known crystalline forms V or VI, unlike a recent CB sample. Part of these triglycerides is in the form IV instead. The presence of the latter seems to be a key parameter that favors the deceleration of the transformation to the form VI, which is responsible for the development of fat bloom.

Published
2022
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2. Experimental and Theoretical Investigations of Low-Dimensional BiFeO3 System for Photocatalytic Applications

Author

Manal Benyoussef, Sébastien Saitzek, Nitul S. Rajput, Matthieu Courty, Mimoun El Marssi, and Mustapha Jouiad

Subjects
photocatalysis, BiFeO3 nanoparticles, high energy ball milling, spray pyrolysis, photoelectrochemical measurements, density functional theory, Chemical technology, TP1-1185, Chemistry, QD1-999
Abstract

We report on the fabrication of sub-20 nm BiFeO3 (BFO) nanoparticles using a solid-state approach and preferential leching process. The nanoparticles were subsequently used to deposit, through spray pyrolysis, BFO thin films in a rhombohedral (R3c) crystallographic structure. Then, systematic investigations of the optical and the photocatalytic properties were conducted to determine the effects of the particles size, the microstructure and the increased surface area on their catalytic performances. Especially, improved optical properties were observed, with an optical bandgap energy of 2.20 eV compared to reported 2.7 eV for the bulk system. In addition, high optical absorption was obtained in the UV–visible light region reaching up to 90% at 400 nm. The photoelectrochemical measurements revealed a high photocurrent density under visible light irradiation. Besides, density functional theory calculations were performed on both bulk and thin film BFO structures, revealing an interesting comparison of the electronic, magnetic, ferroelectric and optical properties for bulk and thin film BFO systems. Both theoretical and experimental findings show that the alignment of the band edges of BFO thin film is coherent with good photocatalytic water splitting potential, making them desirable photoanode materials.

Published
2022
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3. The formulation of a CMC binder/silicon composite anode for Li-ion batteries: from molecular effects of ball milling on polymer chains to consequences on electrochemical performances

Author

Mariama Ndour, Jean-Pierre Bonnet, Sébastien Cavalaglio, Tristan Lombard, Matthieu Courty, Luc Aymard, Cédric Przybylski, Véronique Bonnet, Laboratoire de Glycochimie, des Antimicrobiens et des Agro-ressources - UMR CNRS 7378 (LG2A ), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire réactivité et chimie des solides - UMR CNRS 7314 (LRCS), Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA), Laboratoire des technologies de la microélectronique (LTM ), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA), Commissariat à l'énergie atomique et aux énergies alternatives - Laboratoire d'Electronique et de Technologie de l'Information (CEA-LETI), Direction de Recherche Technologique (CEA) (DRT (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Aix Marseille Université (AMU)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Nantes Université (Nantes Univ)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), and Université de Montpellier (UM)

Subjects
Chemistry (miscellaneous), [CHIM]Chemical Sciences, General Materials Science
Abstract

The semi-synthetic polysaccharide carboxymethylcellulose (CMC) is one of the most studied and effective polymer binders for silicon-based anodes in Li-ion batteries.

Published
2022

4. Theoretical and experimental studies of chitin nanocrystals treated with ionic liquid or deep eutectic solvent to afford nanochitosan sheets

Author

Catalina Ferreira Funes, Benjamin Bouvier, Christine Cézard, Claudia Fuentealba, Arash Jamali, Matthieu Courty, Caroline Hadad, and Albert Nguyen Van Nhien

Subjects
Materials Chemistry, Physical and Theoretical Chemistry, Condensed Matter Physics, Spectroscopy, Atomic and Molecular Physics, and Optics, Electronic, Optical and Magnetic Materials
Published
2023

5. Click Reactions as a Key Step for an Efficient and Selective Synthesis of D-Xylose-Based ILs

Author

Matthieu Courty, Sandrine Bouquillon, Albert Nguyen Van Nhien, Sylvain Gatard, and Nadège Ferlin

Subjects
ionic liquids, D-xylose, click chemistry, Organic chemistry, QD241-441
Abstract

D-Xylose-based ionic liquids have been prepared from D-xylose following a five steps reaction sequence, the key step being a click cycloaddition. These ionic liquids (ILs) have been characterized through classical analytical methods (IR, NMR, mass spectroscopy, elemental analysis) and their stability constants, Tg and Tdec, were also determined. Considering their properties and their hydrophilicity, these compounds could be alternative solvents for chemical applications under mild conditions.

Published
2013
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6. Two-Dimensional Substitution Series $Na_3P_{1-x}Sb_xS_{4-y}Se_y$: Beyond Static Description of Structural Bottlenecks for $Na^{+}$ Transport

Author

Paul Till, Matthias T. Agne, Marvin A. Kraft, Matthieu Courty, Theodosios Famprikis, Michael Ghidiu, Thorben Krauskopf, Christian Masquelier, Wolfgang G. Zeier, Laboratoire réactivité et chimie des solides - UMR CNRS 7314 (LRCS), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Delft University of Technology (TU Delft), Drexel University, Réseau sur le stockage électrochimique de l'énergie (RS2E), Aix Marseille Université (AMU)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Nantes Université (Nantes Univ)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), Physikalisch-Chemisches Institut, and Justus-Liebig-Universität Gießen = Justus Liebig University (JLU)

Subjects
General Chemical Engineering, ddc:540, Materials Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry
Abstract

International audience; Highly conductive solid electrolytes are fundamental for all solid-state batteries with low inner cell resistance. Such fast solid electrolytes are often found by systematic substitution experiments in which one atom is exchanged for another, and corresponding changes in ionic transport are monitored. With this strategy, compositions with the most promising transport properties can be identified fast and reliably. However, the substitution of one element does not only influence the crystal structure and diffusion channel size (static) but also the underlying bonding interactions and with it the vibrational properties of the lattice (dynamic). Since both static and dynamic properties influence the diffusion process, simple one-dimensional substitution series only provide limited insights to the importance of changes in the structure and lattice dynamics for the transport properties. To overcome these limitations, we make use of a two-dimensional substitution approach, investigating and comparing the four single-substitution series Na3P1-xSbxS4, Na3P1-xSbxSe4, Na3PS4-ySey, and Na3SbS4-ySey. Specifically, we find that the diffusion channel size represented by the distance between S/Se ions cannot explain the observed changes of activation barriers throughout the whole substitution system. Melting temperatures and the herein newly defined anharmonic bulk modulus-as descriptors for bonding interactions and corresponding lattice dynamics-correlate well with the activation barriers, highlighting the relevance of lattice softness for the ion transport in this class of fast ion conductors.

Published
2022

7. IL versus DES: Impact on chitin pretreatment to afford high quality and highly functionalizable chitosan

Author

Gaël Huet, Arash Jamali, Caroline Hadad, Jose M. González-Domínguez, Dominique Cailleu, Albert Nguyen Van Nhien, Matthieu Courty, Ministère de l’Education Nationale, de la Formation Professionnelle, de l'Enseignement Supérieur et de la Recherche Scientifique (Maroc), Ministerio de Economía, Industria y Competitividad (España), European Commission, González Domínguez, José Miguel, Courty, Matthieu, Cailleu, D., Nguyen van Nhien, A., González Domínguez, José Miguel [0000-0002-0701-7695], Courty, Matthieu [0000-0003-4017-7727], Cailleu, D. [0000-0002-6894-8522], Nguyen van Nhien, A. [0000-0002-1956-1153], Laboratoire de Glycochimie, des Antimicrobiens et des Agro-ressources - UMR CNRS 7378 (LG2A ), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Reims Champagne-Ardenne (URCA), Laboratoire réactivité et chimie des solides - UMR CNRS 7314 (LRCS), Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA), Plateforme Analytique (PFA), and Université de Picardie Jules Verne (UPJV)

Subjects
Deep eutectic solvent, Hermetia illucens, Polymers and Plastics, Chitin, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Chitosan, chemistry.chemical_compound, Materials Chemistry, Food science, Functionalization, biology, Organic Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, biology.organism_classification, Fatty acid, 0104 chemical sciences, Shrimp, Oleic acid, chemistry, Acetylation, Room temperature ionic liquid, 0210 nano-technology
Abstract

7 figures, 2 tables.-- Supporting information available.-- © 2021. This manuscript version is made available under the CC-BY-NC-ND 4.0 license http://creativecommons.org/licenses/by-nc-nd/4.0/, Chitin is mainly extracted from crustaceans, but this resource is seasonally dependent and can represent a major drawback to satisfy the traceability criterion for high valuable applications. Insect resources are valuable alternatives due to their lower mineral content. However, the deacetylation of chitin into chitosan is still an expensive process. Therefore, we herein compare the impact of both DES/IL-pretreatments on the efficiency of the chemical deacetylation of chitin carried out over two insect sources (Bombyx eri, BE and Hermetia illucens, HI) and shrimp shells (S). The results showed that chitosans obtained from IL-pretreated chitins from BE larva, present lower acetylation degrees (13–17%) than DES-pretreated samples (18–27%). A selective N-acylation reaction with oleic acid has also been performed on the purest and most deacetylated chitosans leading to high substitution degrees (up to 27%). The overall approach validates the proper chitin source and processing methodology to achieve high quality and highly functionalizable chitosan., ANVN thanks the ministère de l'éducation nationale, de l'enseignement supérieur et de la recherche for financial support. J.M.G.-D. greatly acknowledges the Spanish MINEICO for his ‘Juan de la Cierva Incorporation' contract, and associated research funds (ref. IJCI-2016-27789), as well as financial support from the regional government of Aragón (Grupo Reconocido DGA T03_17R, FEDER/UE and DGA-T03_20R).

Published
2021

8. A New Superionic Plastic Polymorph of the Na+ Conductor Na3PS4

Author

Benoit Fleutot, Jean-Noël Chotard, Theodosios Famprikis, M. Saiful Islam, Christian Masquelier, James A. Dawson, François Fauth, Emmanuelle Suard, Oliver Clemens, Matthieu Courty, Delft University of Technology (TU Delft), CELLS ALBA, Barcelona 08290, Spain, University of Stuttgart, Institut Laue-Langevin (ILL), Laboratoire réactivité et chimie des solides - UMR CNRS 7314 (LRCS), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA), Advanced Lithium Energy Storage Systems - ALISTORE-ERI (ALISTORE-ERI), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and University of Bath [Bath]

Subjects
Materials science, Leverage (negotiation), Condensed matter physics, General Chemical Engineering, Biomedical Engineering, Ionic conductivity, General Materials Science, [CHIM.MATE]Chemical Sciences/Material chemistry, Electrical conductor, Conductor
Abstract

International audience; Na3PS4 is one of the most promising Na+ conductors, relevant for applications that can leverage its high ionic conductivity, such as solid-state batteries. Currently, two crystalline phases of the material have been identified, and it has been thought to melt above 500 degrees C. In contrast, based on diffraction, ab initio simulations, impedance spectroscopy, and thermal analysis, we show that Na3PS4 remains solid above this temperature and transforms to a third polymorph, gamma, exhibiting fast-ion conduction and an orthorhombic crystal structure. We show that the fast Na+-conduction is associated with rotational motion of the thiophosphate polyanions pointing to a plastic crystal. These findings are of major importance for the development and understanding of new polyanion-based solid electrolytes.

Published
2019

9. Insights into the Rich Polymorphism of the Na

Author

Theodosios, Famprikis, Houssny, Bouyanfif, Pieremanuele, Canepa, Mohamed, Zbiri, James A, Dawson, Emmanuelle, Suard, François, Fauth, Helen Y, Playford, Damien, Dambournet, Olaf J, Borkiewicz, Matthieu, Courty, Oliver, Clemens, Jean-Noël, Chotard, M Saiful, Islam, and Christian, Masquelier

Subjects
Article
Abstract

Solid electrolytes are crucial for next-generation solid-state batteries, and Na3PS4 is one of the most promising Na+ conductors for such applications, despite outstanding questions regarding its structural polymorphs. In this contribution, we present a detailed investigation of the evolution in structure and dynamics of Na3PS4 over a wide temperature range 30 < T < 600 °C through combined experimental–computational analysis. Although Bragg diffraction experiments indicate a second-order phase transition from the tetragonal ground state (α, P4̅21c) to the cubic polymorph (β, I4̅3m) above ∼250 °C, pair distribution function analysis in real space and Raman spectroscopy indicate remnants of a tetragonal character in the range 250 < T < 500 °C, which we attribute to dynamic local tetragonal distortions. The first-order phase transition to the mesophasic high-temperature polymorph (γ, Fddd) is associated with a sharp volume increase and the onset of liquid-like dynamics for sodium-cations (translational) and thiophosphate-polyanions (rotational) evident by inelastic neutron and Raman spectroscopies, as well as pair-distribution function and molecular dynamics analyses. These results shed light on the rich polymorphism of Na3PS4 and are relevant for a range host of high-performance materials deriving from the Na3PS4 structural archetype.

Published
2021

10. Insights into the rich polymorphism of the Na+ ion conductor Na3PS4 from the perspective of variable-temperature diffraction and spectroscopy

Author

Damien Dambournet, Helen Y. Playford, Pieremanuele Canepa, Houssny Bouyanfif, Matthieu Courty, Mohamed Zbiri, Emmanuelle Suard, Jean-Noël Chotard, Saiful Islam, Christian Masquelier, François Fauth, Theodosios Famprikis, Olaf J. Borkiewicz, and James A. Dawson

Subjects
Phase transition, Tetragonal crystal system, symbols.namesake, Crystallography, Materials science, symbols, Fast ion conductor, Pair distribution function, Raman spectroscopy, Spectroscopy, Ground state, Inelastic neutron scattering
Abstract

Solid electrolytes are crucial for next generation solid state batteries and Na3PS4 is one of the most promising Na+ conductors for such applications. In this contribution, we present a detailed investigation of the evolution in structure and dynamics of Na3PS4 under the effect of temperature in the range 30 < T < 600 °C through combined experimental-computational analysis. Although x ray Bragg diffraction experiments indicate a second order phase transition from the tetragonal ground state (α, P-421c) to the cubic polymorph (β, I-43m), pair distribution function analysis in real space and Raman spectroscopy indicate remnants of tetragonal character in the range 250 < T < 500 °C which we attribute to dynamic local tetragonal distortions. The first order phase transition to the mesophasic high temperature polymorph (γ, Fddd) is associated with a sharp volume increase and the onset of liquid like diffusive dynamics for sodium-cations (translative) and thiophosphate-polyanions (rotational) evident by inelastic neutron- and Raman- spectroscopies, as well as pair-distribution function and molecular dynamics. These results shed light on the rich polymorphism in Na3PS4 and are relevant for a host of high performance materials deriving from the Na3PS4 structural archetype.

Published
2021

11. The Polymorphs of the Na+ Ion Conductor Na3PS4 from the Perspective of Variable Temperature Diffraction and Spectroscopy

Author

Mohamed Zbiri, Saiful Islam, Emmanuelle Suard, Houssny Bouyanfif, Theodosios Famprikis, Helen Y. Playford, Olaf J. Borkiewicz, Christian Masquelier, Matthieu Courty, James A. Dawson, Damien Dambournet, Pieremanuele Canepa, Jean-Noël Chotard, and François Fauth

Subjects
Phase transition, Tetragonal crystal system, symbols.namesake, Materials science, Fast ion conductor, symbols, Analytical chemistry, Pair distribution function, Spectroscopy, Ground state, Raman spectroscopy, Inelastic neutron scattering
Abstract

Solid electrolytes are crucial for next generation solid state batteries and Na3PS4 is one of the most promising Na+ conductors for such applications. In this contribution, we present a detailed investigation of the evolution in structure and dynamics of Na3PS4 under the effect of temperature in the range 30 < T < 600 °C through combined experimental-computational analysis. Although x ray Bragg diffraction experiments indicate a second order phase transition from the tetragonal ground state (α, P-421c) to the cubic polymorph (β, I-43m), pair distribution function analysis in real space and Raman spectroscopy indicate remnants of tetragonal character in the range 250 < T < 500 °C which we attribute to dynamic local tetragonal distortions. The first order phase transition to the mesophasic high temperature polymorph (γ, Fddd) is associated with a sharp volume increase and the onset of liquid like diffusive dynamics for sodium-cations (translative) and thiophosphate-polyanions (rotational) evident by inelastic neutron- and Raman- spectroscopies, as well as pair-distribution function and molecular dynamics. These results shed light on the rich polymorphism in Na3PS4 and are relevant for a host of high performance materials deriving from the Na3PS4 structural archetype.

Published
2021

12. Insights into the Rich Polymorphism of the Na+ Ion Conductor Na3PS4 from the Perspective of Variable-Temperature Diffraction and Spectroscopy

Author

Emmanuelle Suard, M. Saiful Islam, Houssny Bouyanfif, Olaf J. Borkiewicz, Jean-Noël Chotard, Mohamed Zbiri, Theodosios Famprikis, Matthieu Courty, Christian Masquelier, Oliver Clemens, François Fauth, James A. Dawson, Helen Y. Playford, Pieremanuele Canepa, Damien Dambournet, Laboratoire réactivité et chimie des solides - UMR CNRS 7314 (LRCS), Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), University of Bath [Bath], Advanced Lithium Energy Storage Systems - ALISTORE-ERI (ALISTORE-ERI), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Université de Pau et des Pays de l'Adour (UPPA)-Université de Nantes (UN)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Laboratoire de Physique de la Matière Condensée - UR UPJV 2081 (LPMC), Université de Picardie Jules Verne (UPJV), National University of Singapore (NUS), Institut Laue-Langevin (ILL), ILL, Newcastle University [Newcastle], ALBA Synchrotron light source [Barcelone], STFC Rutherford Appleton Laboratory (RAL), Science and Technology Facilities Council (STFC), PHysicochimie des Electrolytes et Nanosystèmes InterfaciauX (PHENIX), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Argonne National Laboratory [Lemont] (ANL), University of Stuttgart, Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), and Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)

Subjects
Phase transition, Materials science, General Chemical Engineering, 02 engineering and technology, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, symbols.namesake, Tetragonal crystal system, Chemical structure, Materials Chemistry, Fast ion conductor, Spectroscopy, Bragg's law, Pair distribution function, General Chemistry, Lattices, [CHIM.MATE]Chemical Sciences/Material chemistry, Atmospheric temperature range, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Crystallography, Phase transitions, Raman spectroscopy, symbols, Group theory, 0210 nano-technology
Abstract

International audience; Solid electrolytes are crucial for next-generation solid-state batteries, and Na 3 PS 4 is one of the most promising Na + conductors for such applications, despite outstanding questions regarding its structural polymorphs. In this contribution, we present a detailed investigation of the evolution in structure and dynamics of Na 3 PS 4 over a wide temperature range 30 < T < 600°C through combined experimental−computational analysis. Although Bragg diffraction experiments indicate a second-order phase transition from the tetragonal ground state (α, P4̅ 2 1 c) to the cubic polymorph (β, I4̅ 3m) above ∼250°C, pair distribution function analysis in real space and Raman spectroscopy indicate remnants of a tetragonal character in the range 250 < T < 500°C, which we attribute to dynamic local tetragonal distortions. The first-order phase transition to the mesophasic high-temperature polymorph (γ, Fddd) is associated with a sharp volume increase and the onset of liquid-like dynamics for sodium-cations (translational) and thiophosphate-polyanions (rotational) evident by inelastic neutron and Raman spectroscopies, as well as pair-distribution function and molecular dynamics analyses. These results shed light on the rich polymorphism of Na 3 PS 4 and are relevant for a range host of high-performance materials deriving from the Na 3 PS 4 structural archetype.

Published
2021

13. Carbon-Loaded Flexible Electrode Films for Li-O2 Cells: Preparation, Porosity, Homogeneity and Electrochemical Characterization

Author

Matthieu Courty, Christine Surcin, Caroline Gaya, Dominique Larcher, and Alejandro A. Franco

Subjects
chemistry.chemical_classification, Materials science, Chemical engineering, chemistry, Electrode, Homogeneity (physics), chemistry.chemical_element, Texture (crystalline), Polymer, Leaching (metallurgy), Porosity, Electrochemistry, Carbon
Abstract

Porous (up to 70 vol. %) self-standing flexible carbon/polymer (Ketjen Black / PVdF-HFP) film electrodes are produced by leaching out a plasticizer-porogen agent (DBP = DiButyl Phtalate) from precursor films (80% ³ DBP w% ³ 40%). Textural analysis reveals that i) these films exhibit copious initial macroporosity, ii) extra open macro- and then meso-porosity are created along the leaching, iii) this leaching process impacts the internal films texture resulting in a partial closing of the pre-existing porosity, iv) only films with the lowest initial DBP contents (≤ 60 w%) are homogeneous in composition/porosity/texture. In Li/O2 cells, the first discharge capacities of these films are compared to those calculated assuming a total filling of this porosity by electrochemically formed solid Li2O2 (2700 mAh.cm-3 of pores). Up to 80 % of the maximum capacity can be reached (i.e. 80 % of the porosity filled by Li2O2), confirming the positive attributes of mixed interconnected macro/meso porosity. This is further emphasized by the very low capacities obtained with electrodes having similar porosity vol. % but totally different internal texture (GDL). These conclusions can be made despite a large discrepancy in the data, even for homogeneous films, due to reproducibility issues intrinsic to the system.

Published
2020

14. Mechanochemical synthesis and ion transport properties of Na3OX (X = Cl, Br, I and BH4) antiperovskite solid electrolytes

Author

Matthieu Courty, Christian Masquelier, Oliver Clemens, Ulas Kudu, Theodosios Famprikis, Ernest Ahiavi, James A. Dawson, M. Saiful Islam, Laboratoire réactivité et chimie des solides - UMR CNRS 7314 (LRCS), Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Université de Pau et des Pays de l'Adour (UPPA)-Université de Nantes (UN)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Advanced Lithium Energy Storage Systems - ALISTORE-ERI (ALISTORE-ERI), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), and Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)

Subjects
Borohydride, Materials science, Ab initio, Energy Engineering and Power Technology, 02 engineering and technology, Electrolyte, Molecular dynamics, 010402 general chemistry, 01 natural sciences, Ion, Antiperovskite, Synthesis, Ionic conductivity, Fast ion conductor, [CHIM]Chemical Sciences, SDG 7 - Affordable and Clean Energy, Electrical and Electronic Engineering, Physical and Theoretical Chemistry, Ion transporter, Renewable Energy, Sustainability and the Environment, 021001 nanoscience & nanotechnology, Ball-milling, 0104 chemical sciences, Dielectric spectroscopy, Physical chemistry, 0210 nano-technology
Abstract

The push towards the development of next-generation solid-state batteries has motivated the search for novel solid electrolyte materials. Sodium antiperovskites represent a structural family of ion conductors that has emerged as a result, with expected advantages in terms of composition tuning, electrochemical stability, mechanical softness and high ionic conductivity. Here, we report the mechanochemical synthesis of several materials in this structural family, including novel mixed-halide compositions such as Na3OCl0.5(BH4)0.5, Na3OBr0.5(BH4)0.5 Na3OI0.5(BH4)0.5 and Na3OCl0.33Br0.33(BH4)0.33. We rationalize the effect of halide substitution on the structure and ion transport properties of these materials through diffraction, impedance spectroscopy and molecular dynamics. We conclude with a discussion on Na3OBH4, which has recently been reported to be a fast ion conductor, owing to the rotational disorder of the complex superhalide anion BH4−. We are unable to reproduce the reported high ionic conductivity of Na3OBH4 neither by experiment nor ab initio simulation.

Published
2020

15. High reactivity of the nickel-rich LiNi1-x-yMnxCoyO2 layered materials surface towards H2O/CO2 atmosphere and LiPF6-based electrolyte

Author

Dominique Cailleu, Sylvie Grugeon, Stéphane Laruelle, Pierre Tran-Van, Ana Cristina Martinez, Matthieu Courty, Bruno Delobel, Laboratoire réactivité et chimie des solides - UMR CNRS 7314 (LRCS), Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Technocentre Renault [Saint-Quentin-en-Yvelines], RENAULT, Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Université de Pau et des Pays de l'Adour (UPPA)-Université de Nantes (UN)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Plateforme Analytique (PFA), Université de Picardie Jules Verne (UPJV), Technocentre Renault [Guyancourt], Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), and Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)

Subjects
Thermogravimetric analysis, Materials science, Inorganic chemistry, Oxide, Energy Engineering and Power Technology, chemistry.chemical_element, 02 engineering and technology, Electrolyte, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, chemistry.chemical_compound, Reactivity (chemistry), Electrical and Electronic Engineering, Physical and Theoretical Chemistry, ComputingMilieux_MISCELLANEOUS, Renewable Energy, Sustainability and the Environment, Thermal decomposition, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Nickel, chemistry, 13. Climate action, Inductively coupled plasma atomic emission spectroscopy, Hydroxide, 0210 nano-technology
Abstract

Storage of nickel-rich LiNi1-x-yMnxCoyO2 positive active materials under improper environmental conditions brings about undesirable surface reactions causing poor Li-ion cell electrochemical performances and gas generation. In this paper, a detailed stepwise investigation of the increasing reactivity of 532, 622, 811 and 901 NMC materials towards a specific H2O/CO2 atmosphere is reported. Water-soluble salts as lithium carbonate, hydroxide and sulfates are accurately quantified thanks to acid-base titration and inductively coupled plasma atomic emission spectroscopy techniques. On the other hand, the presence of insoluble species as transition metal oxyhydroxides and oxides is unveiled through a thermal decomposition study using thermogravimetric mass spectrometer coupling technique. Their formation and thermal decomposition mechanisms are proposed after careful analysis of the characteristic mass loss and O2, CO2 and H2O evolution profile in the 50–500 °C region. Interestingly, the results also highlight an in situ lithiated layered oxide material reformation reaction. To assess their chemical reactivity towards LiPF6-based electrolyte, the latter was analyzed through 19F nuclear magnetic resonance after storage with various reference salts and 811 NMC. LiPO2F2 is detected from storage tests with Li2CO3, Li2O and Li2SO4, and fluorophosphate-type molecules are detected from LiOH; this experiment can help discriminate between LiOH and Li2O as NMC surface species.

Published
2020

16. New biobased-zwitterionic ionic liquids: efficiency and biocompatibility for the development of sustainable biorefinery processes

Author

Catherine Sarazin, Monica Araya-Farias, Benjamin Bouvier, Christine Cézard, Eric Husson, Ranim Alayoubi, Gaël Huet, Isabelle Gosselin, Caroline Hadad, Matthieu Courty, Romain Roulard, Albert Nguyen Van Nhien, Sylvain Laclef, Laboratoire de Glycochimie, des Antimicrobiens et des Agro-ressources - UMR CNRS 7378 (LG2A ), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut Galien Paris-Saclay (IGPS), Institut de Chimie du CNRS (INC)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Génie Enzymatique et Cellulaire (GEC), Université de Technologie de Compiègne (UTC)-Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS), Université de Picardie Jules Verne (UPJV), Laboratoire réactivité et chimie des solides - UMR CNRS 7314 (LRCS), Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Université de Reims Champagne-Ardenne (URCA), Laboratoire des Glucides (LG), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Picardie Jules Verne (UPJV), Biologie des Plantes et Innovation - UR UPJV 3900 (BIOPI), Université de Picardie Jules Verne (UPJV)-Transfrontalière BioEcoAgro - UMR 1158 (BioEcoAgro), Université d'Artois (UA)-Université de Liège-Université de Picardie Jules Verne (UPJV)-Université du Littoral Côte d'Opale (ULCO)-Université de Lille-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-JUNIA (JUNIA), Université catholique de Lille (UCL)-Université catholique de Lille (UCL)-Université d'Artois (UA)-Université de Liège-Université du Littoral Côte d'Opale (ULCO)-Université de Lille-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-JUNIA (JUNIA), and Université catholique de Lille (UCL)-Université catholique de Lille (UCL)

Subjects
Biocompatibility, 010402 general chemistry, 01 natural sciences, chemistry.chemical_compound, Hydrolysis, Environmental Chemistry, Organic chemistry, Ethanol fuel, [SDV.IB.BIO]Life Sciences [q-bio]/Bioengineering/Biomaterials, Alkyl, ComputingMilieux_MISCELLANEOUS, chemistry.chemical_classification, 010405 organic chemistry, [SDE.IE]Environmental Sciences/Environmental Engineering, [CHIM.ORGA]Chemical Sciences/Organic chemistry, [SDV.BBM.BM]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Molecular biology, Biorefinery, Pollution, [SDV.MP.BAC]Life Sciences [q-bio]/Microbiology and Parasitology/Bacteriology, 6. Clean water, Yeast, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry, visual_art, Ionic liquid, visual_art.visual_art_medium, Sawdust
Abstract

International audience; A new family of biobased-zwitterionic ionic liquids (ZILs) have been synthesized starting from the renewable resource L-histidine natural amino acid and varying the lengths of the alkyl chains. These ZIL derivatives were firstly studied for their biocompatibility with different microorganisms including bacteria, molds and yeast. The obtained MIC values indicated that all the microorganisms were 5 to 25 times more tolerant to ZIL derivatives than the robust 1-ethyl-3-methylimidazolium acetate [C2mim][OAc] used as a reference. Modeling studies also revealed that the presence of the cation and the anion on the same skeleton together with the length of the N-alkyl chain would govern the biocompatibility of these neoteric solvents. Among the different synthesized ZILs, the N,N′-diethyl derivative has been demonstrated to be a suitable eco-alternative to the classically used [C2mim][OAc] for efficient pretreatment of harwood sawdust leading to a significant improvement of enzymatic saccharification. In addition, with up to a 5% w/v concentration in the culture medium, ZILs did not induce deleterious effects on fermentative yeast growth nor ethanol production.

Published
2020

17. Straightforward extraction and selective bioconversion of high purity chitin from Bombyx eri larva: Toward an integrated insect biorefinery

Author

Virginie Lambertyn, Catherine Sarazin, Arash Jamali, Sylvain Laclef, Albert Nguyen Van Nhien, Monica Araya Farias, Caroline Hadad, Gaël Huet, Matthieu Courty, Isabelle Gosselin, Ranim Alayoubi, Eric Husson, Laboratoire de Glycochimie, des Antimicrobiens et des Agro-ressources - UMR CNRS 7378 (LG2A ), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Génie Enzymatique et Cellulaire (GEC), Université de Technologie de Compiègne (UTC)-Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS), Université de Picardie Jules Verne (UPJV), Laboratoire réactivité et chimie des solides - UMR CNRS 7314 (LRCS), and Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)

Subjects
[SDV.BIO]Life Sciences [q-bio]/Biotechnology, Polymers and Plastics, Bioconversion, Microorganism, Chitin, 02 engineering and technology, 010402 general chemistry, 7. Clean energy, 01 natural sciences, Hydrolysate, chemistry.chemical_compound, Crustacea, Materials Chemistry, Animals, Bombyx, Chromatography, biology, Chemistry, Organic Chemistry, Extraction (chemistry), 021001 nanoscience & nanotechnology, biology.organism_classification, Biorefinery, 0104 chemical sciences, Shrimp, Larva, 0210 nano-technology
Abstract

International audience; Keywords: Chitin Insect biorefinery Room temperature ionic liquid Enzymatic digestibility Fermentescibility A B S T R A C T Chitins of different purity grades (45%, 89.7% and 93.3%) were efficiently extracted from Bombyx eri larva and fully physico-chemically characterized. Compared to commercially available and extracted α-chitin from shrimp shell, the collected data showed that insect chitins had similar characteristics in terms of crystallographic structures (α-chitin), thermal stability and degree of acetylation (> 87%). The major differences lay in the crystallinity indexes (66% vs 75% for shrimp chitin) and in the morphological structures. Furthermore, low ash contents were determined for the insect chitins (1.90% vs 21.73% for shrimp chitin), making this chitin extraction and purification easier, which is highly valuable for an industrial application. Indeed, after only one step (deproteinization), the obtained chitin from Bombyx eri showed higher purity grade than the one extracted from shrimp shells under the same conditions. Insect chitins were then subjected to room temperature ionic liquid (RTIL) pretreatment prior to enzymatic degradation and presented a higher enzymatic digestibility compared to commercial one whatever their purity grade and would be thus a more relevant source for the selective production of N-acetyl-D-glucosamine (899.2 mg/g of chitin-2 steps vs 760 mg/g of chitin com). Moreover, for the first time, the fermentescibility of chitin hydrolysates was demonstrated with Scheffersomyces stipitis used as ethanologenic microorganism.

Published
2020

18. Oxidative decomposition products of synthetic NaFePO4 marićite: nano-textural and electrochemical characterization

Author

Sorina Cretu, Matthieu Courty, Rénald David, Arnaud Demortière, Fabrice Brunet, Camille Crouzet, Nadir Recham, Institut des Sciences de la Terre (ISTerre), and Institut Français des Sciences et Technologies des Transports, de l'Aménagement et des Réseaux (IFSTTAR)-Institut national des sciences de l'Univers (INSU - CNRS)-Institut de recherche pour le développement [IRD] : UR219-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])

Subjects
Monosodium phosphate, Chemistry, 05 social sciences, [SDU.STU]Sciences of the Universe [physics]/Earth Sciences, Maricite, Thermal treatment, Electrochemistry, Decomposition, chemistry.chemical_compound, Geochemistry and Petrology, Iron oxalate, 0502 economics and business, [SDE]Environmental Sciences, Fast ion conductor, 050211 marketing, Iron phosphate, 050203 business & management, Nuclear chemistry
Abstract

International audience; 44 Single-phase marićite, NaFePO4, was synthesized from monosodium phosphate and 45 iron oxalate at 750°C, at atmospheric pressure. Thermal treatment of synthetic marićite in air 46 indicated oxidative decomposition into Na3Fe 3+ 2(PO4)3 nasicon and-Fe2O3 at temperatures 47 above 225°C. Intergrowth of the reaction products is found to occur at the nanoscale without 48 identified crystallographic relationship with the marićite precursor. Electrochemical activity of 49 the reaction product is confirmed with the reversible insertion of one Na at 2.55 V vs Na + /Na 0. 50 Keywords: sodium iron phosphate; marićite; sodium-ion batteries; oxidative decomposition; 51 NASICON 52 53 54

Published
2019

19. Three-Dimensional Printing of a LiFePO4/Graphite Battery Cell via Fused Deposition Modeling

Author

Hugues Tortajada, Alexis Maurel, Michel Armand, Kalappa Prashantha, Matthieu Courty, Sylvie Grugeon, Stéphane Panier, Benoit Fleutot, Loic Dupont, Laboratoire réactivité et chimie des solides - UMR CNRS 7314 (LRCS), and Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)

Subjects
Materials science, lcsh:Medicine, 02 engineering and technology, Electrolyte, 010402 general chemistry, Electrochemistry, 01 natural sciences, Article, law.invention, chemistry.chemical_compound, Batteries, law, [CHIM]Chemical Sciences, Graphite, Ceramic, lcsh:Science, Separator (electricity), Multidisciplinary, Fused deposition modeling, Lithium iron phosphate, lcsh:R, 021001 nanoscience & nanotechnology, Mechanical engineering, 0104 chemical sciences, Chemical engineering, chemistry, visual_art, Electrode, visual_art.visual_art_medium, lcsh:Q, 0210 nano-technology
Abstract

Among the 3D-printing technologies, fused deposition modeling (FDM) represents a promising route to enable direct incorporation of the battery within the final 3D object. Here, the preparation and characterization of lithium iron phosphate/polylactic acid (LFP/PLA) and SiO2/PLA 3D-printable filaments, specifically conceived respectively as positive electrode and separator in a lithium-ion battery is reported. By means of plasticizer addition, the active material loading within the positive electrode is raised as high as possible (up to 52 wt.%) while still providing enough flexibility to the filament to be printed. A thorough analysis is performed to determine the thermal, electrical and electrochemical effect of carbon black as conductive additive in the positive electrode and the electrolyte uptake impact of ceramic additives in the separator. Considering both optimized filaments composition and using our previously reported graphite/PLA filament for the negative electrode, assembled and “printed in one-shot” complete LFP/Graphite battery cells are 3D-printed and characterized. Taking advantage of the new design capabilities conferred by 3D-printing, separator patterns and infill density are discussed with a view to enhance the liquid electrolyte impregnation and avoid short-circuits.

Published
2019

20. Polymorphism in Li4Zn(PO4)2 and Stabilization of its Structural Disorder to Improve Ionic Conductivity

Author

Jean-Marie Tarascon, Gwenaëlle Rousse, Sujoy Saha, Daniel Alves Dalla Corte, Matthieu Courty, Ignacio Blazquez Alcover, Université Pierre et Marie Curie - Paris 6 (UPMC), Chaire Chimie du solide et énergie, Chimie du solide et de l'énergie (CSE), Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Université de Pau et des Pays de l'Adour (UPPA)-Université de Nantes (UN)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Laboratoire réactivité et chimie des solides - UMR CNRS 7314 (LRCS), Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Collège de France - Chaire Chimie du solide et énergie, Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA), and Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Materials science, Crystal chemistry, General Chemical Engineering, 02 engineering and technology, General Chemistry, Crystal structure, Conductivity, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 0104 chemical sciences, Crystallography, Polymorphism (materials science), Materials Chemistry, Fast ion conductor, [CHIM]Chemical Sciences, Ionic conductivity, Orthorhombic crystal system, 0210 nano-technology, Monoclinic crystal system
Abstract

International audience; Realization of the vulnerability of current rechargeable battery systems drives the research of solid electrolytes. In the search for a new Li ion conductor, we explore the rich crystal chemistry of Li 4 Zn(PO 4) 2 which presents a low temperature monoclinic (α-) and a high temperature orthorhombic (β-) polymorph. We solved the crystal structure of the β-phase and found that it has a disordered Li/Zn-sublattice while showing the largest conductivity; however it could not be stabilized at room temperature by quenching. We discovered that the partial substitution of Zn 2+ with Ga 3+ in Li 4-x Zn 1-x Ga x (PO 4) 2 first leads to an intermediate β' phase. Increasing the Ga content to 0.5 mol pfu. enables to stabilize the pure β-phase at room temperature, which exhibits a conductivity by several orders of magnitudes higher than the pristine sample. The crystal structures of the new β'/β-phases have been solved to elucidate the conduction mechanism, which confirms the high sensitivity of ionic conductivity on disorder.

Published
2018

21. A New Phase of the Na+ Ion Conductor Na3PS4

Author

François Fauth, James A. Dawson, Saiful Islam, Benoit Fleutot, Matthieu Courty, Jean-Noël Chotard, Christian Masquelier, Theodosios Famprikis, and Emmanuelle Suard

Subjects
Diffraction, Materials science, Scattering, Chemical physics, Phase (matter), Neutron diffraction, Fast ion conductor, Density functional theory, Orthorhombic crystal system, Thermal analysis
Abstract

Solid electrolytes are crucial for next‑generation solid‑state batteries and Na3PS4 is one of the most promising Na+ conductors for such applications. At present, two phases of Na3PS4 have been identified and it had been thought to melt above 500 °C. In contrast, we show that it remains solid above this temperature and transforms into a third polymorph, γ, exhibiting superionic behavior. We propose an orthorhombic crystal structure for γ‑Na3PS4 based on scattering density analysis of diffraction data and density functional theory calculations. We show that the Na+ superionic behavior is associated with rotational motion of the thiophosphate polyanions pointing to a rotor phase, based on ab initio molecular dynamics simulations and supported by high‑temperature synchrotron and neutron diffraction, thermal analysis and impedance spectroscopy. These findings are of importance for the development of new polyanion‑based solid electrolytes.

Published
2019

22. Poly(Ethylene Oxide)−LiTFSI Solid Polymer Electrolyte Filaments for Fused Deposition Modeling Three-Dimensional Printing

Author

Sylvie Grugeon, Stéphane Panier, Hugues Tortajada, Matthieu Courty, Benoit Fleutot, Alexis Maurel, Loic Dupont, Carine Davoisne, and Michel Armand

Subjects
chemistry.chemical_classification, Materials science, Fused deposition modeling, Renewable Energy, Sustainability and the Environment, Oxide, Electrolyte, Polymer, Condensed Matter Physics, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, law.invention, chemistry.chemical_compound, Chemical engineering, chemistry, law, Three dimensional printing, Materials Chemistry, Electrochemistry, Poly ethylene
Abstract

Additive manufacturing technologies open the way to the direct-integration of electronics and solid-state battery within the final 3D object. Here, a 3D printable polyethylene oxide/lithium bis(trifluoromethanesulfonyl)imide (PEO/LiTFSI) filament (2.18 × 10−3 S cm−1 at 90 °C) optimized to be used as solid polymer electrolyte in a lithium-ion battery is produced to feed a fused deposition modeling (FDM) 3D-printer. Due to its relatively poor mechanical properties compared to classical polymer filament such as polylactic acid (PLA), deep modifications of the 3D-printer were implemented in order to facilitate its printability. The solid polymer electrolyte thermal, structural, morphological, mechanical and electrical characterization is reported. Interestingly, using three different electrochemical impedance spectroscopy sample holders (lateral, sandwich and interdigitated-comb), we demonstrate that conductivity values differs for a same sample, highlighting the PEO chains orientation effect on the conductivity measurements.

Published
2020

23. Temperature dependence of structural and transport properties for Na3V2(PO4)2F3 and Na3V2(PO4)2F2.5O0.5

Author

Philippe Veber, Annelise Brüll, François Fauth, Benoit Fleutot, Christian Masquelier, Rénald David, Laurence Croguennec, Thibault Broux, Matthieu Courty, Institut de Chimie de la Matière Condensée de Bordeaux (ICMCB), Université de Bordeaux (UB)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire réactivité et chimie des solides - UMR CNRS 7314 (LRCS), Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Université de Pau et des Pays de l'Adour (UPPA)-Université de Nantes (UN)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), European Synchrotron Radiation Facility (ESRF), Advanced Lithium Energy Storage Systems - ALISTORE-ERI (ALISTORE-ERI), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), the European Union’s Horizon 2020 research and innovation program under grant agreement No. 646433-NAIADES., ANR-10-LABX-0076,STORE-EX,Laboratory of excellency for electrochemical energy storage(2010), ANR-13-DESC-0001,SODIUM,Batteries à ions sodium pour des robots télécommandés(2013), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), and Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)

Subjects
Electrode material, Phase transition, Valence (chemistry), Materials science, General Chemical Engineering, Analytical chemistry, chemistry.chemical_element, 02 engineering and technology, General Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, Electrochemistry, 7. Clean energy, 01 natural sciences, Oxygen, 0104 chemical sciences, Ion, chemistry, Materials Chemistry, Fluorine, Ionic conductivity, 0210 nano-technology
Abstract

International audience; Among polyanionic-based electrode materials developed for Na-ion batteries, one of the most promising families turns out to be Na3V2(PO4)2F3–yOy (0 ≤ y ≤ 2). Here, we present the influence of the oxygen substitution for fluorine on the structural and transport properties of Na3V2(PO4)2F3–yOy, as a function of temperature, through the comparison of the two compositions y = 0 and y = 0.5. An order–disorder phase transition is observed, whatever the content in oxygen, in relation with changes in the ionic conductivity and thus with the mobility of the Na+ ions within the tunnels of the tridimensional structure. The richer the content in oxygen in Na3V2(PO4)2F3–yOy, the higher is the electronic conductivity, in relation with the mixed valence state V3+/V4+ within the bioctahedral units V2O8F3–yOy, and the better are the electrochemical performances in Na-ion batteries.

Published
2018

24. An all-solid state NASICON sodium battery operating at 200 °C

Author

Vincent Seznec, Fabien Lalère, Sylvain Boulineau, Matthieu Courty, Virginie Viallet, Christian Masquelier, and Jean Bernard Leriche

Subjects
Battery (electricity), Materials science, Renewable Energy, Sustainability and the Environment, Inorganic chemistry, Analytical chemistry, Energy Engineering and Power Technology, Sodium-ion battery, Spark plasma sintering, Electrolyte, Electrochemistry, Electrode, Fast ion conductor, Ionic conductivity, Electrical and Electronic Engineering, Physical and Theoretical Chemistry
Abstract

An all-solid state symmetric monolithic sodium ion battery operating at 200 °C is described, using NASICON-type electrodes and electrolyte. Na3V2(PO4)3 is used at both electrodes as the active material while Na3Zr2Si2PO12 stands the role of the Na+ solid electrolyte. Both compositions present order-disorder phase transitions and present decent ionic conductivity properties, 1.5 × 10−3 S cm−1 and 1.9 × 10−4 S cm−1 at 200 °C for Na3Zr2Si2PO12 and Na3V2(PO4)3, respectively. The full battery (560 μm in thickness) was assembled in a 10′ single step by spark plasma sintering at 900 °C. The electrochemical characteristics at high temperature (200 °C) were evaluated thanks to a new experimental set-up. The battery operates at 1.8 V with 85% of the theoretical capacity attained at C/10 with satisfactory capacity retention, for an overall energy density of 1.87 × 10−3 W h cm−2 and a capacity of 1.04 mA h cm−2.

Published
2014

25. A new sensitive organic/inorganic hybrid material based on titanium oxide for the potentiometric detection of iron(III)

Author

Pascal Rouge, Christel Gervais, Pascal Sonnet, Matthieu Becuwe, Alexandra Dassonville-Klimpt, Matthieu Courty, E. Baudrin, Spectroscopie, Modélisation, Interfaces pour L'Environnement et la Santé (SMiLES), Laboratoire de Chimie de la Matière Condensée de Paris (LCMCP), Université Pierre et Marie Curie - Paris 6 (UPMC)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)

Subjects
Magnetic Resonance Spectroscopy, Materials science, Surface Properties, Iron, Inorganic chemistry, Potentiometric titration, Oxide, 02 engineering and technology, 010402 general chemistry, Potentiometric detection, 01 natural sciences, Biomaterials, chemistry.chemical_compound, Colloid and Surface Chemistry, Microscopy, Electron, Transmission, X-Ray Diffraction, Spectroscopy, Fourier Transform Infrared, Fourier transform infrared spectroscopy, Thermal analysis, Hybrid material, Titanium, Titanium oxide, Organophosphorous coupling agent, Substrate (chemistry), [CHIM.MATE]Chemical Sciences/Material chemistry, Iron(III), 021001 nanoscience & nanotechnology, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, chemistry, Titanium dioxide, Potentiometry, 0210 nano-technology
Abstract

International audience; The formation of a new hybrid material based on titanium dioxide as inorganic support and containing an iron organochelator (ICL670) is described. An organophosphorous coupling agent was used to graft the organic molecule on the oxide surface. The attachment of the organic substrate was well-confirmed by FTIR (DRIFT), solid-state 31P and 13C CPMAS NMR, thermal analysis and the integrity of the structural and morphological parameters were verified using XRD and TEM analyses. The interaction between the material and dissolved iron(III) was also investigated through potentiometric measurements and demonstrated the interest of this new non-siliceous based hybrid material. The obtained linear evolution of the open circuit potential from 10−2 to 10−6 mol L−1 can be used for the analytical detection of iron(III).

Published
2012

26. Synthesis, Structure, and Electrochemical Properties of Na3MB5O10 (M = Fe, Co) Containing M2+in Tetrahedral Coordination

Author

Gwenaëlle Rousse, Daniel Alves Dalla Corte, Robert Dominko, Florian Strauss, Jean-Marie Tarascon, Matthieu Courty, Moulay Tahar Sougrati, Advanced Lithium Energy Storage Systems - ALISTORE-ERI (ALISTORE-ERI), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), National Institute of Chemistry, Université Pierre et Marie Curie - Paris 6 (UPMC), Collège de France - Chaire Chimie du solide et énergie, Chimie du solide et de l'énergie (CSE), Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Laboratoire réactivité et chimie des solides - UMR CNRS 7314 (LRCS), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Chaire Chimie du solide et énergie, Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Université de Pau et des Pays de l'Adour (UPPA)-Université de Nantes (UN)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), and Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)

Subjects
Diffraction, Chemistry, Sodium, Inorganic chemistry, chemistry.chemical_element, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, Electrochemistry, 01 natural sciences, Redox, Synchrotron, Cathode, 0104 chemical sciences, law.invention, Inorganic Chemistry, Crystallography, law, Mössbauer spectroscopy, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, 0210 nano-technology, Boron
Abstract

International audience; In the search for new cathode materials for sodium ion batteries, the exploration of polyanionic compounds has led to attractive candidates in terms of high redox potential and cycling stability. Herein we report the synthesis of two new sodium transition metal pentaborates Na 3 MB 5 O 10 (M = Fe, Co), where Na 3 FeB 5 O 10 represents the first sodium iron borate reported at present. By means of synchrotron X-ray diffraction, we reveal a layered structure consisting of pentaborate B 5 O 10 groups connected through M 2+ in tetrahedral coordination, providing possible three-dimensional Na-ion migration pathways. Inspired by these structural features we examined the electrochemical performances versus sodium and show that Na 3 FeB 5 O 10 is active at an average potential of 2.5 V vs. Na + /Na 0 , correlated to the Fe 3+ /Fe 2+ redox couple as deduced from ex situ Mössbauer measurements. This contrasts with Na 3 CoB 5 O 10 which is electrochemical inactive. Moreover, we show that their electrochemical performances are kinetically limited as deduced by complementary AC/DC conductivity measurements, hence confirming once again the complexity in designing highly performant borate-based electrodes.

Published
2016

27. Tetrabutylammonium prolinate-based ionic liquids:A combined asymmetric catalysis, antimicrobial toxicity and biodegradation assessment

Author

Nadège Ferlin, Annette Haiß, Sandrine Bouquillon, Milan Pour, Brid Quilty, Sylvain Gatard, Albert Nguyen Van Nhien, Matthieu Courty, Nicholas Gathergood, Klaus Kümmerer, Mukund Ghavre, Institut de Chimie Moléculaire de Reims - UMR 7312 (ICMR), SFR Condorcet, Université de Reims Champagne-Ardenne (URCA)-Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS)-Université de Reims Champagne-Ardenne (URCA)-Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS)-SFR CAP Santé (Champagne-Ardenne Picardie Santé), Université de Reims Champagne-Ardenne (URCA)-Université de Picardie Jules Verne (UPJV)-Université de Reims Champagne-Ardenne (URCA)-Université de Picardie Jules Verne (UPJV)-Université de Reims Champagne-Ardenne (URCA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire réactivité et chimie des solides - UMR CNRS 7314 (LRCS), Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Laboratoire de Glycochimie, des Antimicrobiens et des Agro-ressources - UMR CNRS 7378 (LG2A ), and Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Chiral ionic liquids, Double bond, Enantioselective hydrogenation, General Chemical Engineering, Carbon-carbon double bonds, Decomposition temperature, One-Step, 010402 general chemistry, 01 natural sciences, chemistry.chemical_compound, Asymmetric catalysis, Unsaturated ketones, Organic chemistry, [CHIM]Chemical Sciences, Closed bottle biodegradation tests, chemistry.chemical_classification, 010405 organic chemistry, Chemistry, Tetrabutylammonium hydroxide, Thermal decomposition, Enantioselective synthesis, Tetrabutylammonium hydroxides, General Chemistry, Biodegradation, Antimicrobial, 0104 chemical sciences, Ionic liquid
Abstract

International audience; Chiral ionic liquids (CILs) tetrabutylammonium-(S)-prolinate, tetrabutylammonium-(R)-prolinate and tetrabutylammonium trans-4-hydroxy-(S)-prolinate were investigated as chiral additives in the Pd-catalyzed enantioselective hydrogenation of α,β-unsaturated ketones. These CILs were easily prepared in one step from the aminoacid and tetrabutylammonium hydroxide and characterized (NMR, IR, optical rotation, elemental analysis, DSC, viscosity, decomposition temperature). The research strategy was to assess the antimicrobial toxicity (>20 strains) and biodegradability (OECD 301D) of the CILs at the same time as undertaking the asymmetric catalysis study. The Pd-catalyzed enantioselective hydrogenation of the carbon–carbon double bond of α,β-unsaturated ketones under mild conditions (room temperature, 1 atm of H2) in different solvents with CILs present. The best results were obtained in i-PrOH after 18 hours of reaction with a i-PrOH/IL ratio of 5. While all three CILs have low antimicrobial toxicity to a wide range of bacteria and fungi, tetrabutylammonium-(S)-prolinate, tetrabutylammonium-(R)-prolinate and tetrabutylammonium trans-4-hydroxy-(S)-prolinate did not pass the Closed Bottle biodegradation test.

Published
2013

28. Click Reactions as a Key Step for an Efficient and Selective Synthesis of D-Xylose-Based ILs

Author

Sylvain Gatard, Albert Nguyen Van Nhien, Nadège Ferlin, Sandrine Bouquillon, Matthieu Courty, Institut de Chimie Moléculaire de Reims - UMR 7312 (ICMR), SFR Condorcet, Université de Reims Champagne-Ardenne (URCA)-Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS)-Université de Reims Champagne-Ardenne (URCA)-Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS)-SFR CAP Santé (Champagne-Ardenne Picardie Santé), Université de Reims Champagne-Ardenne (URCA)-Université de Picardie Jules Verne (UPJV)-Université de Reims Champagne-Ardenne (URCA)-Université de Picardie Jules Verne (UPJV)-Université de Reims Champagne-Ardenne (URCA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Glycochimie, des Antimicrobiens et des Agro-ressources - UMR CNRS 7378 (LG2A ), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire réactivité et chimie des solides - UMR CNRS 7314 (LRCS), and Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)

Subjects
ionic liquids, D-xylose, click chemistry, Pharmaceutical Science, Xylose, 010402 general chemistry, Mass spectrometry, 01 natural sciences, Methylation, TP Chemical technology, Catalysis, Article, Analytical Chemistry, lcsh:QD241-441, chemistry.chemical_compound, Reaction sequence, Drug Stability, lcsh:Organic chemistry, Drug Discovery, Organic chemistry, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, Cycloaddition Reaction, 010405 organic chemistry, Chemistry, Organic Chemistry, Cycloaddition, 0104 chemical sciences, Chemistry (miscellaneous), Elemental analysis, Ionic liquid, Thermogravimetry, Click chemistry, Molecular Medicine, Copper
Abstract

International audience; D-Xylose-based ionic liquids have been prepared from D-xylose following a five steps reaction sequence, the key step being a click cycloaddition. These ionic liquids (ILs) have been characterized through classical analytical methods (IR, NMR, mass spectroscopy, elemental analysis) and their stability constants, Tg and Tdec, were also determined. Considering their properties and their hydrophilicity, these compounds could be alternative solvents for chemical applications under mild conditions.

Published
2013

29. Preparation and characterization of LiNi0.5Mn1.5O4−δ thin films taking advantage of correlations with powder samples behavior

Author

Emmanuel Baudrin, Matthieu Courty, Liping Wang, Hong Li, Xuejie Huang, Beijing National Laboratory for Condensed Matter Physics, Chinese Academy of Sciences [Beijing] (CAS), Laboratoire réactivité et chimie des solides - UMR CNRS 7314 (LRCS), Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Laboratoire de Glycochimie, des Antimicrobiens et des Agro-ressources - UMR CNRS 7378 (LG2A ), and Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Materials science, Renewable Energy, Sustainability and the Environment, Annealing (metallurgy), [SDV]Life Sciences [q-bio], Spinel, Analytical chemistry, Energy Engineering and Power Technology, chemistry.chemical_element, 02 engineering and technology, Electrolyte, engineering.material, 010402 general chemistry, 021001 nanoscience & nanotechnology, Microstructure, 01 natural sciences, Oxygen, 0104 chemical sciences, Pulsed laser deposition, chemistry, engineering, Electrical and Electronic Engineering, Physical and Theoretical Chemistry, Thin film, 0210 nano-technology, Stoichiometry
Abstract

International audience; The high voltage spinel LiNi0.5Mn1.5O 4-δ films were obtained by pulsed laser deposition. The effects of oxygen deficiency, annealing treatment, and film thickness on microstructure, morphology and electrochemical properties were investigated. We showed that tuning the oxygen pressure and annealing treatment allows modifying the oxygen film stoichiometry. Trying to determine the oxygen stoichiometry in thin films, a series of oxygen-deficient spinel "LiNi0.5Mn 1.5O4-δ" powder samples by quench steps from different temperatures were prepared. It is demonstrated that powders and thin films presenting similar cell parameters, namely related to the oxygen stoichiometry, show similar electrochemical profiles. Meanwhile, the compatibility of electrolyte with substrate and the stability of the target were also investigated.

Published
2013

30. Syntheses and characterisation of hydrophobic ionic liquids containing trialkyl(2-ethoxy-2-oxoethyl)ammonium or N-(1-methylpyrrolidyl-2-ethoxy-2-oxoethyl)ammonium cations

Author

Patrick Fricoteaux, Matthieu Courty, Albert Nguyen-Van-Nhien, Aminou Mohamadou, Stéphanie Boudesocque, Ahmed Messadi, Laurent Dupont, Institut de Chimie Moléculaire de Reims - UMR 7312 (ICMR), SFR Condorcet, Université de Reims Champagne-Ardenne (URCA)-Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS)-Université de Reims Champagne-Ardenne (URCA)-Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS)-SFR CAP Santé (Champagne-Ardenne Picardie Santé), Université de Reims Champagne-Ardenne (URCA)-Université de Picardie Jules Verne (UPJV)-Université de Reims Champagne-Ardenne (URCA)-Université de Picardie Jules Verne (UPJV)-Université de Reims Champagne-Ardenne (URCA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire d'ingénierie des systèmes macromoléculaires (LISM), Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Aix Marseille Université (AMU), Laboratoire des Glucides (LG), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Picardie Jules Verne (UPJV), Laboratoire réactivité et chimie des solides - UMR CNRS 7314 (LRCS), Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Université de Reims Champagne-Ardenne (URCA)-Université de Picardie Jules Verne (UPJV)-Université de Reims Champagne-Ardenne (URCA)-Université de Picardie Jules Verne (UPJV)-Université de Reims Champagne-Ardenne (URCA)-Centre National de la Recherche Scientifique (CNRS), Aix Marseille Université (AMU)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Laboratoire réactivité et chimie des solides (LRCS), Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS), Université de Reims Champagne-Ardenne (URCA)-Institut de Chimie du CNRS (INC)-SFR CAP Santé (Champagne-Ardenne Picardie Santé), Université de Reims Champagne-Ardenne (URCA)-Université de Reims Champagne-Ardenne (URCA)-Centre National de la Recherche Scientifique (CNRS)-SFR Condorcet, Université de Reims Champagne-Ardenne (URCA)-Centre National de la Recherche Scientifique (CNRS)-Université de Reims Champagne-Ardenne (URCA)-Centre National de la Recherche Scientifique (CNRS), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Reims Champagne-Ardenne (URCA)-SFR CAP Santé (Champagne-Ardenne Picardie Santé), Université de Reims Champagne-Ardenne (URCA)-Université de Picardie Jules Verne (UPJV)-Université de Reims Champagne-Ardenne (URCA)-Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS)-SFR Condorcet, and Université de Reims Champagne-Ardenne (URCA)-Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS)-Université de Reims Champagne-Ardenne (URCA)-Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Tetrafluoroborate, Bis(trifluoromethylsulfonyl)imide, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, chemistry.chemical_compound, Glycine-betaine, Polymer chemistry, Materials Chemistry, Organic chemistry, Ammonium, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry, Imide, Dicyanamide, Spectroscopy, Alkyl, ComputingMilieux_MISCELLANEOUS, chemistry.chemical_classification, 010405 organic chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Hydrophobic ionic liquid, Condensed Matter Physics, Atomic and Molecular Physics, and Optics, 0104 chemical sciences, Electronic, Optical and Magnetic Materials, chemistry, Ionic liquid, Alkoxy group, Electrochemical window
Abstract

International audience; A series of salts based on ethyl ester betaine derivatives [trialkyl(2-ethoxy-2-oxoethyl)ammonium or N-(1-methylpyrrolidyl-2-ethoxy-2-oxoethyl)ammonium cations] with alkyl chains [ethyl, n-propyl and n-butyl] have been synthesized. These cations generate hydrophobic ionic liquids with bis(trifluoromethylsulfonyl)imide, tetrafluoroborate or dicyanamide anions. The influence of the alkyl chain length and the chemical nature of the counteranion on physicochemical properties such as density, melting point, glass transition and decomposition temperatures, viscosity, and electrochemical window have been investigated.

Published
2013

31. Calix[4]arene-modified silica nanoparticles for the potentiometric detection of iron (III) in aqueous solution

Author

Pascal Sonnet, Dominique Cailleu, Christel Gervais, Pascal Rouge, Matthieu Becuwe, Alexandra Dassonville-Klimpt, Matthieu Courty, E. Baudrin, Laboratoire réactivité et chimie des solides - UMR CNRS 7314 (LRCS), Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Laboratoire des Glucides (LG), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Picardie Jules Verne (UPJV), Spectroscopie, Modélisation, Interfaces pour L'Environnement et la Santé (SMiLES), Laboratoire de Chimie de la Matière Condensée de Paris (LCMCP), Université Pierre et Marie Curie - Paris 6 (UPMC)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Aqueous solution, Chemistry, Ligand, General Chemical Engineering, 010401 analytical chemistry, Potentiometric titration, Inorganic chemistry, 02 engineering and technology, General Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Coupling reaction, Calix[4]arene, 0104 chemical sciences, Nucleophile, Covalent bond, Potentiometry, ICL670, Fourier transform infrared spectroscopy, 0210 nano-technology, Hybrid material, Iron sensor
Abstract

International audience; This article aims to present the synthesis and the characterization of a novel hybrid material, based on silica nanoparticles, and which can be used as a sensitive element for the electrochemical detection of iron (III). This material was obtained by grafting an iron ligand-based calix[4]arene structure onto nanosized silica particles. The covalent anchoring of the chelator was obtained by nucleophilic coupling reaction between the modified calix[4]arene and the chloropropyl functionalized silica. The grafting reaction was confirmed by FTIR (DRIFT), solid-state 13C Cross-Polarization MAS (CPMAS) NMR and thermal analysis. The interaction between the material and the dissolved iron (III) was demonstrated though potentiometric measurements. A linear evolution of the open circuit potential, which can be used analytically for iron (III) detection, has been obtained.

Published
2012

32. Catalytic coatings on stainless steel prepared by sol–gel route

Author

Dimitri Truyen, Matthieu Courty, Pierre Alphonse, Florence Ansart, Centre interuniversitaire de recherche et d'ingenierie des matériaux (CIRIMAT), Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC), Institut National Polytechnique de Toulouse - Toulouse INP (FRANCE), Université Toulouse III - Paul Sabatier - UT3 (FRANCE), and Centre National de la Recherche Scientifique - CNRS (FRANCE)

Subjects
Catalytic film, Boehmite, Materials science, Matériaux, Alumina, Nanoparticle, 02 engineering and technology, Sol–gel, 010402 general chemistry, Peptization, 01 natural sciences, Catalysis, chemistry.chemical_compound, Specific surface area, Materials Chemistry, Thermal stability, Thixotropy, Sol-gel, Metallurgy, Metals and Alloys, Surfaces and Interfaces, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Chemical engineering, chemistry, Alkoxide, 0210 nano-technology
Abstract

International audience; Stainless steel (flat and microstructured) substrates have been coated with sol–gel catalysts made up of metal nanoparticles (Rh, Ni, Pt) dispersed on alumina and alumina–ceria supports. The aluminum monohydroxyde (boehmite) sols were synthesized by hot hydrolysis/peptization of an aluminum alkoxide (Yoldas method). It is shown that the rheological properties of the sol, especially the thixotropy, play a key role on the homogeneity and the quality of the film deposited on the metal substrate. The catalyst layers have a very good adhesion, a thickness which can be easily controlled (in the range 0.1 to 10 μm), a large specific surface area and a good mechanical and thermal stability.

Published
2006

33. Platinum/ceria/alumina catalysts on microstructures for carbon monoxide conversion

Author

Yves Schuurman, Pierre Alphonse, Matthieu Courty, Claudine Mirodatos, G. Germani, Institut National Polytechnique de Toulouse - INPT (FRANCE), Université Toulouse III - Paul Sabatier - UT3 (FRANCE), Centre National de la Recherche Scientifique - CNRS (FRANCE), IRCELYON, ProductionsScientifiques, Institut de recherches sur la catalyse et l'environnement de Lyon (IRCELYON), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Centre interuniversitaire de recherche et d'ingenierie des matériaux (CIRIMAT), Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC), Institut de recherches sur la catalyse (IRC), Centre National de la Recherche Scientifique (CNRS), and Institut National Polytechnique de Toulouse - Toulouse INP (FRANCE)

Subjects
Materials science, Hydrogen purification, Matériaux, Inorganic chemistry, Proton exchange membrane fuel cell, chemistry.chemical_element, 02 engineering and technology, Activation energy, 010402 general chemistry, 7. Clean energy, 01 natural sciences, Hydrogen purifier, Catalysis, Water-gas shift reaction, Adsorption, Water-gas shift, Catalyst coating, Water gas, [CHIM.CATA] Chemical Sciences/Catalysis, Microreactors -Kinetics, General Chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, 021001 nanoscience & nanotechnology, 0104 chemical sciences, sol–gel, chemistry, 0210 nano-technology, Platinum
Abstract

International audience; Platinum/ceria/alumina catalysts have been prepared by a sol–gel method and coated in the microchannels of stainless steel platelets. These catalysts are very active for the water-gas shift reaction between 300 and 400°C. Moreover, they are non-pyrophoric and thus well suited for the purification of hydrogen for PEM fuel cells. The obtained coatings show good adherence and catalytic activity. The influence of the amount of platinum and ceria as well as the effect of a binder on the catalytic performance has been investigated. The samples have been characterized before reaction by XRD, SEM and by N2 adsorption measurements. The kinetics, free from internal diffusion limitations, over these thin films have been described by a power law rate equation. An activation energy of 86 kJ/mol has been found and at 260 °C the TOF corresponds to 0.6 ± 0.1 s−1 for all investigated samples. The superior activity of the platelets compared to the powder samples is attributed to the diffusion limitations inside the powder pellets. Thus catalysts deposited on microstructured platelets lead to a better platinum utilization.

Published
2005

34. Surface and porosity of nanocrystalline boehmite xerogels

Author

Pierre Alphonse, Matthieu Courty, Institut National Polytechnique de Toulouse - Toulouse INP (FRANCE), Université Toulouse III - Paul Sabatier - UT3 (FRANCE), Centre National de la Recherche Scientifique - CNRS (FRANCE), Centre interuniversitaire de recherche et d'ingenierie des matériaux (CIRIMAT), Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut National Polytechnique (Toulouse) (Toulouse INP), and Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)

Subjects
Boehmite, Materials science, Surface Properties, Matériaux, Mineralogy, Specific surface area, Aluminum Hydroxide, 02 engineering and technology, 010402 general chemistry, Peptization, 01 natural sciences, Nitric Acid, Sensitivity and Specificity, law.invention, [SPI.MAT]Engineering Sciences [physics]/Materials, Biomaterials, Colloid and Surface Chemistry, Microscopy, Electron, Transmission, X-Ray Diffraction, law, Aluminum Oxide, Crystallization, Particle Size, Porosity, PSD, Hydrolysis, Temperature, 021001 nanoscience & nanotechnology, Nanocrystalline material, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Nanostructures, Chemical engineering, Comparative plot, Crystallite, Particle size, 0210 nano-technology, Gels
Abstract

Boehmite xerogels are prepared by hydrolysis of Al(OC4H9)3 followed by peptization with HNO3 (H+/Al = 0, 0.07, 0.2). XRD and TEM show that these gels are made of nanosized crystals (5-9 nm in width and 3 nm thick). According to the amount of acid, no significant differences are found in size and shape, but only in the spatial arrangement of the crystallites. Nitrogen adsorption-desorption isotherms of nonpeptized gels are of type IV, whereas isotherms of peptized gels are of type I. These isotherms are analyzed by the t-plot method. The majority of pore volume results from intercrystalline mesopores, but the peptized gels also contain intercrystalline micropores. The particle packing is very dense for the gel peptized with H+/Al = 0.2 (porosity = 0.26), but it is less dense in non-peptized gel (porosity = 0.44). Heating these gels under vacuum creates, from 250 degrees C onwards, an intracrystalline microporosity resulting from the conversion of boehmite into transition alumina. But heating also causes intercrystalline micropores collapsing. The specific surface area increases up to a limit temperature (300 degrees C for nonpeptized gels and 400 degrees C for peptized) beyond which sintering of the particles begins and the surface decreases. The PSD are calculated assuming a cylindrical pore geometry and using the corrected Kelvin equation proposed by Kruk et al. Peptized xerogels give a monomodal distribution with a maximum near 2 nm and no pores are larger than 6 nm. Nonpeptized gels have a bimodal distribution with a narrow peak near to 2 nm and a broad unsymmetrical peak with a maximum at 4 nm. Heating in air above 400 degrees C has a strong effect on the porosity. As the temperature increases, there is a broadening of the distribution and a marked decrease of small pores (below 3 nm). However, even after treatment at 800 degrees C, micropores are still present.

Published
2005

35. Structure and thermal behavior of nanocrystalline boehmite

Author

Pierre Alphonse, Matthieu Courty, Institut National Polytechnique de Toulouse - Toulouse INP (FRANCE), Université Toulouse III - Paul Sabatier - UT3 (FRANCE), Centre National de la Recherche Scientifique - CNRS (FRANCE), Centre interuniversitaire de recherche et d'ingenierie des matériaux (CIRIMAT), Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut National Polytechnique (Toulouse) (Toulouse INP), and Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)

Subjects
Boehmite, Materials science, Matériaux, chemistry.chemical_element, Mineralogy, 02 engineering and technology, Activation energy, 010402 general chemistry, Peptization, 01 natural sciences, Transition alumina, Aluminium, Specific surface area, medicine, Dehydration, Physical and Theoretical Chemistry, Instrumentation, [CHIM.MATE]Chemical Sciences/Material chemistry, Computer simulation, 021001 nanoscience & nanotechnology, Condensed Matter Physics, medicine.disease, Nanocrystalline material, 0104 chemical sciences, chemistry, Chemical engineering, Non-isothermal kinetics, Particle, 0210 nano-technology
Abstract

International audience; First, the structural features of nanocrystalline boehmite synthesized by hydrolysis of aluminum sec-butoxide according to the Yoldas method are reported. The nanosized boehmite consists of rectangular platelets averaging 8 by 9 nm and 2–3 nm in thickness which contain a large excess of water. Dehydration by heating under vacuum induced an increase in the specific surface area, down to a minimum water content ( 0.2 H2O per Al2O3); values up to 470 m2/g can be reached. However this enlargement of specific surface area only results from water loss, the surface area remaining constant. The particle morphology, the excess of water, as well as the specific surface area, depend on the amount of acid used for the peptization during the synthesis. Second, a comprehensive investigation of the dehydration kinetics is presented. The simulations of the non-isothermal experiments at constant heating rates show that thermally stimulated transformation of nanocrystalline boehmite into alumina can be accurately modeled by a 4-reaction mechanism involving: (I) the loss of physisorbed water, (II) the loss of chemisorbed water, (III) the conversion of boehmite into transition alumina, (IV) the dehydration of transition alumina (loss of residual hydroxyl groups). The activation energy of each step is found to be very similar for experiments done in various conditions (heating rate, atmosphere, kind of sample,...).

Published
2005

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